Poly(4-vinylpyridine) derivatives alkylated with dimethylsulfate, octylbromide and dodecylbromide were synthesized. Counter ions in the polymer salts were substituted with bis(2-ethylhexyl)sulfosuccinate. The solutions of the polyelectrolyte-surfactant complexes in the mixtures of decane with chloroform were studied by dynamic light scattering. At high decane content all the complexes have expanded coil conformations. The increase of chloroform content over 60 vol.% leads to folding of the coils to globule state and to the appearance of the second peak on the DLS curves corresponding to the small fraction of large particles with hydrodynamic radii R ca 40-80 nm. The ability of the synthesized complexes to stabilize reversed emulsions was studied. It was shown that polymer complexes of AOT with comb-like polycations stabilize emulsions of water in 4:1 mixture of decane with chloroform. Addition of sodium chloride to the system markedly increases stabilizing effect of the comb-like polycations with AOT. (C) 2011 Elsevier Ltd. All rights reserved.